CN103275382A - Irradiation crosslinked polyethylene blending material for artificial joints and preparation method thereof - Google Patents
Irradiation crosslinked polyethylene blending material for artificial joints and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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Abstract
The invention provides an irradiation crosslinked polyethylene blending self-reinforcing material for artificial joints and a preparation method thereof. The polyethylene blending material for artificial joints is prepared by blending low molecular weight polyethylene (LMWPE) and irradiation crosslinked ultrahigh molecular weight polyethylene (UHMWPE). The preparation method comprises the following steps: (1) preparing irradiation crosslinked UHMWPE, (2) preparing LMWPE master batch, (3) preparing irradiation crosslinked UHMWPE/LMWPE blending material, and (4) vibration injection molding. The irradiation crosslinked polyethylene blending self-reinforcing material for artificial joints has the advantages that the relative content of UHMWPE in polyethylene blend is improved to the maximum extent during the process of vibration injection molding and the excellent performance is reserved, a shish-kebab self-reinforcing structure is formed in the inner part due to vibration injection molding, and tensile property, impact strength and wear-resisting property are improved remarkably. Therefore, the irradiation crosslinked polyethylene blending self-reinforcing material is suitable for joint prosthesis implant material.
Description
Technical field
The invention belongs to field of biomedical polymer materials.Particularly, the present invention relates to a kind of joint prosthesis IXPE blend material and preparation method thereof.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) since coming out the sixties in 19th century, has been successfully applied to hip joint and knee prosthesis as the joint prosthesis implant material.The key factor that influences joint prosthesis implant material performance and work-ing life is wearability, oxidative stability and mechanical property.Through domestic and international years of researches, obtaining remarkable progress aspect raising abrasion resistance properties and the oxidative stability.Specifically, wearability can improve by irradiation crosslinking technological, the UHMWPE artificial joint material is after high dosage irradiation is handled, and its wear rate never-6.9 ± 0.6 mg/MC of irradiation drops to-1.4 ± 0.4 mg/MC(Oral E. Biomaterials 2010; 31:7051-7060), yet irradiation process can produce free radical, remaining free radical with the long-term contact process of air in, can cause oxidative degradation, further damage its mechanical property.Improving aspect the material oxidation stability, a kind of method is melting treatment behind the employing irradiation, this process can cause degree of crystallinity to descend, damage the mechanical property (Oral E. In:Kurtz S, editor. The second edition of the UHMWPE handbook. Elsevier 2009:197-204) of irradiation UHMWPE.Another method is to add free radical scavenger, vitamin-E (VE) the most effectively wherein, after adding VE in the irradiation UHMWPE artificial joint material, its oxidation index drops to 0.44 ± 0.06 (Oral E. Biomaterials 2004 from 3.74 ± 0.16; 25:5515-5522).Melting process behind the irradiation has been avoided in the adding of free radical scavenger, has kept the mechanical property of irradiation UHMWPE, still, the existence of irradiation process still more or less infringement the mechanical property of UHMWPE joint material.Meanwhile, the patient who accepts joint replacement surgery is rejuvenation trend, and patient's activity intensity is bigger, so the mechanical property of joint prosthesis implant material is had higher requirement.At present do not cause very big concern as yet for the research that improves the mechanical property aspect, so that the research of this aspect seems is particularly important.
Present stage to the research that improves the mechanical property aspect more successful be to adopt the vibration injection moulding to prepare self-reinforced polyethylene material (Ling Xu, Zhong-Ming Li*. ACS Appl. Mater. Interfaces 2012; 4:1521-1529).This method is by obtaining polyethylene (PE) blend of well processed flowability to satisfy the requirement of vibration injection moulding with UHMWPE and low molecular weight polyethylene (LMWPE) blend, because UHMWPE has great viscosity, weight relative content is the highest can only reach 40 % for it, the sample of vibration injection moulding is compared with the compression moulding sample of routine, mechanical property and impact property have obtained improving significantly, but wearability is not greatly improved.In order to satisfy artificial joint material to the requirement of over-all properties, need further to improve mechanical property, and equal extent improve its wearability.Because UHMWPE has excellent mechanical property and shock strength, its abrasion resistance properties is far superior to LMWPE, improve the relative content of UHMWPE in the PE blend, can utilize the excellent properties of UHMWPE to greatest extent, make this material better application in the joint prosthesis field.Yet, in the vibration injection molding process, further improve the UHMWPE relative content and will cause and can't process.
Summary of the invention
In order to overcome above-mentioned prior art defective, the object of the present invention is to provide a kind of joint prosthesis IXPE blend material.This polyethylene blend material portion has within it formed shish-kebab (shish-kebab) self-reinforced structure, has strengthened mechanical property and shock strength to a greater degree, has also improved its wearability simultaneously.
Another object of the present invention is to provide described polyethylene blend preparation methods.
The present invention is used for realizing that the technical scheme of above-mentioned purpose is as follows:
On the one hand, the invention provides a kind of joint prosthesis IXPE blend material, described polyethylene blend material is made by low molecular weight polyethylene and cross-linking radiation super-high molecular weight polythene blending.Adopt the method for cross-linking radiation can improve the relative content of UHMWPE in the PE blend, because UHMWPE has excellent mechanical property and shock strength, its abrasion resistance properties is far superior to LMWPE, improve the relative content of UHMWPE in the PE blend, can utilize the excellent properties of UHMWPE to greatest extent, make this material better application in the joint prosthesis field.
Preferably, the relative molecular weight of wherein said low molecular weight polyethylene is 8 ~ 15 myriagram/moles, be understandable that, described polyethylene blend material is used for joint prosthesis, low molecular weight polyethylene and ultrahigh molecular weight polyethylene(UHMWPE) are the bio-medical level, and the mass percent that described cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) accounts for the polyethylene blend material is 50% ~ 60%.
Preferably, described cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) is to make by the following method: with relative molecular mass 500 ~ 600 myriagram/moles, particle dia is that the ultrahigh molecular weight polyethylene powder of 100 ~ 400 μ m carries out cross-linking radiation through energetic ray, irradiation dose is chosen for 30 ~ 200 kGy, is optimum with 40 kGy.
On the other hand, the invention provides above-mentioned polyethylene blend preparation methods, described preparation method may further comprise the steps:
(1) cross-linking radiation UHMWPE preparation: ultrahigh molecular weight polyethylene powder is carried out high-energy ray irradiation handle, obtain the cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE), gained cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) is placed under the protection of inert gas, to prevent its oxidative degradation, preferably, rare gas element is nitrogen;
(2) LMWPE masterbatch preparation: will be that 1:49 carries out mechanically mixing with the mass ratio without ultrahigh molecular weight polyethylene powder and the low molecular weight polyethylene of radiation treatment, and add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued to stir 60 ~ 80 minutes down at 135 ~ 140 ℃; Gained solution is injected in the ethanol of room temperature, the ethanol volume is 2 ~ 3 times of solution, make that to contain the UHMWPE mass percent be that the UHMWPE/LMWPE blend of 2 % is separated out, filter then, be not higher than 0.01% of own wt with filtering the gained solid being dried to water content below 100 ℃, obtain the low molecular weight polyethylene masterbatch at last;
(3) cross-linking radiation UHMWPE/LMWPE blend preparation: after step (1) gained cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) and step (2) gained low molecular weight polyethylene masterbatch mechanically mixing, place the twin screw extruder melt blending to extrude, then this blend is forced cooling and pelletizing, and dry below 100 ℃, be dried to water content and be not higher than 0.01% of own wt;
(4) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding.
Preferably, the relative molecular mass of described pre-irradiation UHMWPE is 500 ~ 600 myriagram/moles, and UHMWPE powder diameter is 100 ~ 400 μ m; The relative molecular weight of described LMWPE is 8 ~ 15 myriagram/moles.
In above-mentioned steps (1), preferably, described energetic ray is electron beam ray or gamma-rays, more preferably is the electron beam ray, adopts electron beam irradiation to be because its output rating is big, production efficiency is high, is suitable for large batch of radiation processing.The irradiation of this energetic ray can form cross-linking set in molecular chain, long chain molecule effectively is limited in the cross-linking set, spreads in system thereby reduce it, effectively reduces melt viscosity, makes further raising UHMWPE relative content become possibility.
In above-mentioned steps (1), preferably, described irradiation dose is 30 ~ 200 kGy, is optimum with 40 kGy again wherein.The dosage of irradiation (energy) is extremely important, and the content of UHMWPE to a certain degree is subjected to the influence of irradiation dose in the described polyethylene blend, and irradiation dose is excessive or too small, all can influence the flowability of blend, thus the normal moulding of influence vibration injection moulding.Without the sample of irradiation, on the prerequisite that guarantees the normal moulding of vibration injection moulding, wherein UHMWPE extra best best percentage ratio can only reach 40%, and through the sample of 200 kGy cross-linking radiations, wherein UHMWPE extra best best percentage ratio can reach 60%.At the sample of 30 ~ 200kGy scope radiation treatment, not only in its outer shish-kebab structure of finding, the shish-kebab structure appears in internal layer equally; Wherein when 40 kGy irradiation, the mass percent of UHMWPE reaches 50%, than the pure UHMWPE that does not add LMWPE compression moulding, the tensile property of described blend, shock strength and wearability all are significantly improved, and it is optimum that its performance reaches in all samples.
In above-mentioned steps (3), preferably, the conveying compression section of described forcing machine, melt zone and metering zone temperature are set at 150 ~ 170 ℃, 180 ~ 200 ℃ and 185 ~ 195 ℃ respectively, and engine speed is set at 130 ~ 150 rev/mins, and feed rate is 6 ~ 8 rev/mins.
In above-mentioned steps (4), preferably, the barrel temperature of injection moulding machine is 170 ~ 210 ℃ in the described vibration injection moulding, nozzle temperature is 200 ~ 210 ℃, the hot runner temperature is set at 190 ~ 220 ℃, and die temperature is 40 ~ 50 ℃, and dwell pressure is set at 70 ~ 90 MPa.
The present invention has following remarkable advantage compared with prior art:
(1) method of the present invention is by the electron beam to irradiate crosslinked technology, the UHMWPE long chain molecule is limited in the cross-linking set, reduce its diffusion in the system, the limited entanglement effect that slows down between molecular chain, thereby significantly reduce the viscosity of UHMWPE/LMWPE blend, make when adopting the vibration injection moulding, the UHMWPE relative content becomes possibility in the raising blend, thereby utilizes the excellent properties of UHMWPE to greatest extent.
(2) cross-linking set that in irradiation process, forms of polyethylene blend, compare more stable with the physical entanglement point, thereby the easier maintenance orientation of orientation molecular chain makes vibration injection moulding batten except the shish-kebab crystal is arranged at skin, and the shish-kebab structure has still appearred in internal layer.By the IXPE blend material of the present invention's preparation, tensile strength has reached 81.2 MPa, compares with compression moulding UHMWPE and has improved 194 %, and shock strength has increased 9.5 kJ/m
2, abrasion resistance properties is down to 5.3 mg/MC from 8.1 mg/MC, and the range of decrease is 34.6 %.
Description of drawings
Fig. 1 is the scanning electron microscope diagram sheet of comparative example 4 skins of the present invention (from the surface to 1mm);
Fig. 2 is the scanning electron microscope diagram sheet of the embodiment of the invention 2 skins (from the surface to 1mm);
Fig. 3 is the scanning electron microscope diagram sheet of the embodiment of the invention 4 skins (from the surface to 1mm);
Fig. 4 is the small angle X ray scattering figure (SAXS) of the embodiment of the invention 2 and comparative example 5 skins and internal layer, a
1, a
2, b
1, b
2Represent embodiment 2 skins, embodiment 2 internal layers, comparative example 5 skins, comparative example 5 internal layers respectively.
Embodiment
Specifically describe below by the present invention of embodiment; be necessary to be pointed out that at this following examples just are used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to the foregoing invention content still belong to protection scope of the present invention.
In addition, it is pointed out that the material in following examples is weight part.
Embodiment 1
(1) cross-linking radiation UHMWPE preparation: the UHMWPE powder is used the electron beam radiation treatment in air, irradiation dose is chosen for 30 kGy, then the sample behind the irradiation is placed under the nitrogen protection, in case the oxidation degraded.
(2) LMWPE masterbatch preparation: will be that 1:49 carries out mechanically mixing with the mass ratio without ultrahigh molecular weight polyethylene powder and the low molecular weight polyethylene of radiation treatment, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued to stir 60 minutes down at 135 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(3) cross-linking radiation UHMWPE/LMWPE blend preparation: behind the UHMWPE and LMWPE masterbatch mechanically mixing with radiation treatment, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 170 ℃, 200 ℃ and 190 ℃, engine speed is set at 150 rev/mins, feed rate is 8 rev/mins, then this blend is forced cooling and pelletizing, and be dried to water content 100 ℃ of following dryings and be not higher than 0.01% of own wt;
(4) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, and injecting machine material tube and nozzle temperature are set at 210 ℃, 190 ℃, and the hot runner temperature is set at 210 ℃, and die temperature is 40 ℃, and dwell pressure is set at 90 MPa.
Embodiment 2
(1) cross-linking radiation UHMWPE preparation: the UHMWPE powder is used the electron beam radiation treatment in air, irradiation dose is chosen for 40 kGy, then the sample behind the irradiation is placed under the nitrogen protection, in case the oxidation degraded.
(2) LMWPE masterbatch preparation: will be that 1:49 carries out mechanically mixing with the mass ratio without ultrahigh molecular weight polyethylene powder and the low molecular weight polyethylene of radiation treatment, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued to stir 70 minutes down at 140 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(3) cross-linking radiation UHMWPE/LMWPE blend preparation: behind the UHMWPE and LMWPE masterbatch mechanically mixing with radiation treatment, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 160 ℃, 190 ℃ and 185 ℃, engine speed is set at 140 rev/mins, feed rate is 7 rev/mins, then this blend is forced cooling and pelletizing, and be dried to water content 100 ℃ of following dryings and be not higher than 0.01% of own wt;
(4) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, and injecting machine material tube and nozzle temperature are set at 200 ℃, 200 ℃, and the hot runner temperature is set at 220 ℃, and die temperature is 50 ℃, and dwell pressure is set at 70 MPa.
(1) cross-linking radiation UHMWPE preparation: the UHMWPE powder is used the electron beam radiation treatment in air, irradiation dose is chosen for 100 kGy, then the sample behind the irradiation is placed under the nitrogen protection, in case the oxidation degraded.
(2) LMWPE masterbatch preparation: will be that 1:49 carries out mechanically mixing with the mass ratio without ultrahigh molecular weight polyethylene powder and the low molecular weight polyethylene of radiation treatment, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued to stir 60 minutes down at 140 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(3) cross-linking radiation UHMWPE/LMWPE blend preparation: behind the UHMWPE and LMWPE masterbatch mechanically mixing with radiation treatment, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 170 ℃, 200 ℃ and 195 ℃, engine speed is set at 130 rev/mins, feed rate is 8 rev/mins, then this blend is forced cooling and pelletizing, and be dried to water content 100 ℃ of following dryings and be not higher than 0.01% of own wt;
(4) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, injecting machine material tube and nozzle temperature are set at 180 ℃, 210 ℃, the hot runner temperature is set at 210 ℃, and die temperature is 45 ℃, and dwell pressure is set at 80 MPa.
Embodiment 4
(1) cross-linking radiation UHMWPE preparation: the UHMWPE powder is used the electron beam radiation treatment in air, irradiation dose is chosen for 200 kGy, then the sample behind the irradiation is placed under the nitrogen protection, in case the oxidation degraded.
(2) LMWPE masterbatch preparation: will be that 1:49 carries out mechanically mixing with the mass ratio without ultrahigh molecular weight polyethylene powder and the low molecular weight polyethylene of radiation treatment, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued to stir 80 minutes down at 138 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(3) cross-linking radiation UHMWPE/LMWPE blend preparation: behind the UHMWPE and LMWPE masterbatch mechanically mixing with radiation treatment, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 165 ℃, 180 ℃ and 190 ℃, engine speed is set at 130 rev/mins, feed rate is 7 rev/mins, then this blend is forced cooling and pelletizing, and be dried to water content 100 ℃ of following dryings and be not higher than 0.01% of own wt;
(4) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, and injecting machine material tube and nozzle temperature are set at 210 ℃, 200 ℃, and the hot runner temperature is set at 210 ℃, and die temperature is 40 ℃, and dwell pressure is set at 80 MPa.
Comparative example 1
(1) LMWPE masterbatch preparation: be that 1:49 carries out mechanically mixing with the mass ratio with UHMWPE powder and LMWPE, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued stirring 60 minutes down at 135 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(2) UHMWPE/LMWPE blend preparation: after UHMWPE and LMWPE masterbatch mechanically mixing, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 170 ℃, 200 ℃ and 190 ℃, engine speed is set at 150 rev/mins, feed rate is 8 rev/mins, then this blend is forced cooling and pelletizing, and is dried to water content 100 ℃ of following dryings and is not higher than 0.01% of own wt;
(3) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, and injecting machine material tube and nozzle temperature are set at 210 ℃, 190 ℃, and the hot runner temperature is set at 210 ℃, and die temperature is 40 ℃, and dwell pressure is set at 90 MPa.
Comparative example 2
(1) LMWPE masterbatch preparation: be that 1:49 carries out mechanically mixing with the mass ratio with UHMWPE powder and LMWPE, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued stirring 70 minutes down at 140 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(2) UHMWPE/LMWPE blend preparation: after UHMWPE and LMWPE masterbatch mechanically mixing, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 160 ℃, 190 ℃ and 185 ℃, engine speed is set at 140 rev/mins, feed rate is 7 rev/mins, then this blend is forced cooling and pelletizing, and is dried to water content 100 ℃ of following dryings and is not higher than 0.01% of own wt;
(3) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, and injecting machine material tube and nozzle temperature are set at 200 ℃, 200 ℃, and the hot runner temperature is set at 220 ℃, and die temperature is 50 ℃, and dwell pressure is set at 70 MPa.
Comparative example 3
(1) LMWPE masterbatch preparation: be that 1:49 carries out mechanically mixing with the mass ratio with UHMWPE powder and LMWPE, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued stirring 60 minutes down at 140 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(2) UHMWPE/LMWPE blend preparation: after UHMWPE and LMWPE masterbatch mechanically mixing, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 170 ℃, 200 ℃ and 195 ℃, engine speed is set at 130 rev/mins, feed rate is 8 rev/mins, then this blend is forced cooling and pelletizing, and is dried to water content 100 ℃ of following dryings and is not higher than 0.01% of own wt;
(3) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, injecting machine material tube and nozzle temperature are set at 180 ℃, 210 ℃, the hot runner temperature is set at 210 ℃, and die temperature is 45 ℃, and dwell pressure is set at 80 MPa.
Comparative example 4
(1) LMWPE masterbatch preparation: be that 1:49 carries out mechanically mixing with the mass ratio with UHMWPE powder and LMWPE, add the xylene solution blend until forming homogeneous phase transparent solution, then it is continued stirring 80 minutes down at 138 ℃.Gained solution is injected in the ethanol of room temperature, the ethanol volume is 3 times of solution, and the UHMWPE/LMWPE blend that contains 2 %UHMWPE is separated out, and filters then, will leach thing under 100 ℃ of temperature dry 12 hours;
(2) cross-linking radiation UHMWPE/LMWPE blend preparation: behind the UHMWPE and LMWPE masterbatch mechanically mixing with radiation treatment, place the twin screw extruder melt blending to extrude, specifically fill a prescription as table one, forcing machine carries compression section, melt zone and metering zone temperature to be set at 165 ℃, 180 ℃ and 190 ℃, engine speed is set at 130 rev/mins, feed rate is 7 rev/mins, then this blend is forced cooling and pelletizing, and be dried to water content 100 ℃ of following dryings and be not higher than 0.01% of own wt;
(3) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding, and injecting machine material tube and nozzle temperature are set at 210 ℃, 200 ℃, and the hot runner temperature is set at 210 ℃, and die temperature is 40 ℃, and dwell pressure is set at 80 MPa.
Comparative example 5.
Set of dispense ratio by comparative example in the table one 5 provides carries out the compression molding moulding with material under 200 ℃, clamp time is 2.0 h, prepares pure UHMWPE pressing and is used for performance relatively.
The present invention also adopts scanning electronic microscope to observe to the microscopic pattern of IXPE intermingling material, the results are shown in accompanying drawing 1-3.What accompanying drawing 1-3 represented is under various dose irradiation, with vibration during injection moulding, during maximum level that UHMWPE can reach (Fig. 1, during 0 kGy irradiation, high-content 40 % of UHMWPE; Fig. 2, during 40 kGy irradiation, high-content 50 % of UHMWPE; Fig. 3, during 200 kGy irradiation, high-content 60 % of UHMWPE) the outer scanning electron microscope diagram of corresponding sample, as can be seen, under the shear flow field action, the skin of sample (from the surface to 1mm) has formed shish-kebab (shish-kebab) structure, and the moving field orientation of platelet longshore current is orientated, and this is the immanent cause that material property is improved.
The present invention has also carried out the small angle X ray scattering sign to IXPE intermingling material embodiment 2 and UHMWPE compression moulding sample comparative example 5.We can see UHMWPE carried out cross-linking radiation after, at itself and the skin of the sample (embodiment 2) of LMWPE blend vibration injection moulding and the diffracted signal that shish-kebab all appears in internal layer, illustrate that shish-kebab does not exist only in skin, internal layer (apart from surperficial 1mm ~ 2mm place) exists too.Yet no matter compression moulding UHMWPE still is the diffracted signal that shish-kebab does not all appear in internal layer at skin, illustrates not have the shish-kebab structure.
Use mechanical property, shock strength and the abrasion resistance properties of cross-linking radiation UHMWPE/LMWPE self-reinforced material for the joint prosthesis of probing into the present invention's preparation, utilize ASTM-D 638 to carry out the tensile property test, GB/T 1843-96 carries out the impact property test, the MM-200 abrading machine carries out the polishing machine test, and test result sees Table two.Adopt 40 kGy cross-linking radiations, under the prerequisite that guarantees vibration injection moulding success moulding, UHMWPE content never 40 % of radiation treatment is increased to 50 %, and this material has excellent performance, its tensile strength further is increased to 81.2 MPa, and wear rate further drops to 5.3 mg/MC.Therefore, the present invention proposes a kind of under vibration injection moulding condition, at utmost improve the method for UHMWPE relative content in polyethylene blend, the cross-linking radiation UHMWPE/LMWPE of this method preparation has comprehensive performance as the joint prosthesis implant material.
The prescription of table one embodiment 1-4 and comparative example 1-5
| Embodiment | Irradiation dose | UHMWPE relative content (weight) | LMWPE relative content (weight) |
| 1 | 30 kGy | 50 % | 50 % |
| 2 | 40 kGy | 50 % | 50 % |
| 3 | 100 kGy | 50 % | 50 % |
| 4 | 200 kGy | 60 % | 40% |
| Comparative example 1 | 0 kGy | 10% | 90% |
| Comparative example 2 | 0 kGy | 20% | 80% |
| Comparative example 3 | 0 kGy | 30 % | 70% |
| Comparative example 4 | 0 kGy | 40 % | 60% |
| Comparative example 5 | 0 kGy | 100% | 0% |
The tensile property of table two embodiment 1-4 and comparative example 1-5, impact property and abrasion resistance properties are relatively
| Embodiment | Tensile strength (MPa) | Impact property (kJ/m 2） | Wear rate (mg/MC) |
| 1 | 72.5 | 38.5 | 5.7 |
| 2 | 81.2 | 39.1 | 5.3 |
| 3 | 70.1 | 35.2 | 5.9 |
| 4 | 50.5 | 44.3 | 9.5 |
| Comparative example 1 | 48.1 | 20.7 | 11.6 |
| Comparative example 2 | 59.4 | 26.5 | 9.1 |
| Comparative example 3 | 68.5 | 34.1 | 7.6 |
| Comparative example 4 | 78.4 | 43.1 | 6.1 |
| Comparative example 5 | 27.2 | 29.6 | 8.1 |
Claims (10)
1. a joint prosthesis IXPE blend material is characterized in that being made by low molecular weight polyethylene and cross-linking radiation super-high molecular weight polythene blending.
2. polyethylene blend material according to claim 1 is characterized in that, the relative molecular weight of described low molecular weight polyethylene is 8 ~ 15 myriagram/moles.
3. polyethylene blend material according to claim 1 is characterized in that, the mass percent that described cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) accounts for the polyethylene blend material is 50% ~ 60%.
4. according to each described polyethylene blend material in the claim 1 to 3, it is characterized in that: described cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) is to make by the following method: the ultrahigh molecular weight polyethylene powder of relative molecular mass 500 ~ 600 myriagram/moles is carried out cross-linking radiation through energetic ray, and irradiation dose is chosen for 30 ~ 200 kGy;
Preferably, the granularity of ultrahigh molecular weight polyethylene powder is 100 ~ 400 μ m, and irradiation dose is 40 kGy.
5. prepare described joint prosthesis with the method for IXPE blend material, it is characterized in that, may further comprise the steps:
(1) cross-linking radiation UHMWPE preparation: ultrahigh molecular weight polyethylene powder is carried out high-energy ray irradiation handle, obtain the cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE), gained cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) is placed under the protection of inert gas;
(2) LMWPE masterbatch preparation: will be that 1:49 carries out mechanically mixing with the mass ratio without ultrahigh molecular weight polyethylene powder and the low molecular weight polyethylene of radiation treatment, and add the xylene solution blend until forming homogeneous phase transparent solution, then described homogeneous phase transparent solution is continued to stir 60 ~ 80 minutes down at 135 ~ 140 ℃; The solution that will stir gained again injects the room temperature ethanol of 2 ~ 3 times of amounts of own vol, waiting to contain the UHMWPE mass percent and be the UHMWPE/LMWPE blend of 2 % separates out, filter then, be not higher than 0.01% of own wt with filtering the gained solid being dried to water content below 100 ℃, obtain the low molecular weight polyethylene masterbatch at last;
(3) cross-linking radiation UHMWPE/LMWPE blend preparation: after step (1) gained cross-linking radiation ultrahigh molecular weight polyethylene(UHMWPE) and step (2) gained low molecular weight polyethylene masterbatch mechanically mixing, place the twin screw extruder melt blending to extrude, then this blending extrudant is forced cooling and pelletizing, and be not higher than 0.01% of own wt being dried to water content below 100 ℃;
(4) vibration injection moulding: the above-mentioned dried pellet of extruding is vibrated injection moulding.
6. preparation method according to claim 5 is characterized in that, the relative molecular mass of described pre-irradiation UHMWPE is 500 ~ 600 myriagram/moles, and UHMWPE powder diameter is 100 ~ 400 μ m; The relative molecular weight of described LMWPE is 500 ~ 600 myriagram/moles.
7. according to claim 5 or 6 described preparation methods, it is characterized in that the energetic ray described in the step (1) can be electron beam ray or gamma-rays.
8. according to claim 5 or 6 described preparation methods, it is characterized in that in the step (1), the irradiation dose of described energetic ray is 30 ~ 200 kGy, is optimum with 40 kGy.
9. according to claim 5 or 6 described preparation methods, it is characterized in that, in the step (3), the conveying compression section of described forcing machine, melt zone and metering zone temperature are set at 150 ~ 170 ℃, 180 ~ 200 ℃ and 185 ~ 195 ℃ respectively, engine speed is set at 130 ~ 150 rev/mins, and feed rate is 6 ~ 8 rev/mins.
10. according to claim 5 or 6 described preparation methods, it is characterized in that, the barrel temperature of injection moulding machine is 170 ~ 210 ℃ in the described vibration injection moulding of step (4), nozzle temperature is 200 ~ 210 ℃, the hot runner temperature is set at 190 ~ 220 ℃, die temperature is 40 ~ 50 ℃, and dwell pressure is set at 70 ~ 90 MPa.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709482A (en) * | 2013-12-25 | 2014-04-09 | 四川大学 | Preparation method of high-performance artificial knee joint cushion material |
| CN104277304A (en) * | 2014-10-29 | 2015-01-14 | 安徽省皖捷液压科技有限公司 | Low-friction self-lubricated nozzle |
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| CN107754013A (en) * | 2017-12-04 | 2018-03-06 | 四川大学 | The high crosslinked ultra-high-molecular-weight polyethylene artificial joint material of high antioxygen and preparation method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211195A (en) * | 1996-02-13 | 1999-03-17 | 麻省理工学院 | Radiation and melt treated ultra high molecular weight polyethylene prosthetic devices |
| CN101077917A (en) * | 2007-06-22 | 2007-11-28 | 四川大学 | Super-high molecular weight polythene blending modified compound and preparation method thereof |
-
2013
- 2013-06-21 CN CN201310247665.8A patent/CN103275382B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211195A (en) * | 1996-02-13 | 1999-03-17 | 麻省理工学院 | Radiation and melt treated ultra high molecular weight polyethylene prosthetic devices |
| CN101077917A (en) * | 2007-06-22 | 2007-11-28 | 四川大学 | Super-high molecular weight polythene blending modified compound and preparation method thereof |
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| CN103709482A (en) * | 2013-12-25 | 2014-04-09 | 四川大学 | Preparation method of high-performance artificial knee joint cushion material |
| CN104277304A (en) * | 2014-10-29 | 2015-01-14 | 安徽省皖捷液压科技有限公司 | Low-friction self-lubricated nozzle |
| CN105001486A (en) * | 2015-06-18 | 2015-10-28 | 四川大学 | High-wear-resisting high-strength ultra-high molecular weight polyvinyl artificial articular material and preparation method thereof |
| CN105524334A (en) * | 2016-02-23 | 2016-04-27 | 吉林大学 | Self-reinforced polymer composite and preparation method thereof |
| CN105542286A (en) * | 2016-02-23 | 2016-05-04 | 吉林大学 | Self-modified high polymer material and preparation method thereof |
| CN107754013A (en) * | 2017-12-04 | 2018-03-06 | 四川大学 | The high crosslinked ultra-high-molecular-weight polyethylene artificial joint material of high antioxygen and preparation method |
| CN107754013B (en) * | 2017-12-04 | 2020-11-10 | 四川大学 | High-antioxidant high-crosslinking ultrahigh molecular weight polyethylene artificial joint material and preparation method thereof |
| CN110075350A (en) * | 2019-03-26 | 2019-08-02 | 南京师范大学 | A kind of wear-resisting anti-oxidant joint prosthesis biomaterial |
| CN113122949A (en) * | 2021-05-21 | 2021-07-16 | 浙江千禧龙纤特种纤维股份有限公司 | Ultrahigh molecular weight polyethylene fiber for manufacturing reservoir seepage-proofing paving cloth and preparation method thereof |
| CN113122949B (en) * | 2021-05-21 | 2022-07-15 | 浙江千禧龙纤特种纤维股份有限公司 | Ultra-high molecular weight polyethylene fiber for manufacturing reservoir seepage-proofing laying cloth and preparation method thereof |
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